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Description
Table grapes are very popular in Germany and are on offer most of the year. The majority of table grapes on the German market originate abroad; however, in the last few years an increasing number of local grapes are also being marketed in autumn, from September to October. From the budding of the plants through to the harvest, grapes are exposed to pests and illnesses. Pesticides are therefore commonly employed in commercial cultivation to protect the grapes from pests and to safeguard the harvest. In previous years, however, analyses of table grapes have detected pesticide residues in exceedance of the maximum residue limit (MRL) for pesticides. Therefore, within the scope of the official food control program, table grapes were also analyzed in 2012, including an increased number of samples from local cultivation.
Document Sample
23.01.2013
Pesticide Residues in Table Grapes (Jan – Oct, 2012)
Analytical Background
Table grapes are very popular in Germany and are
on offer most of the year. The majority of table
grapes on the German market originate abroad;
however, in the last few years an increasing num-
ber of local grapes are also being marketed in au-
tumn, from September to October.
From the budding of the plants through to the har-
vest, grapes are exposed to pests and illnesses.
Pesticides are therefore commonly employed in commercial cultivation to
protect the grapes from pests and to safeguard the harvest. In previous
years, however, analyses of table grapes have detected pesticide resi-
dues in exceedance of the maximum residue limit (MRL) for pesticides.
Therefore, within the scope of the official food control program, table
grapes were also analyzed in 2012, including an increased number of
samples from local cultivation.
Summary
Table grapes from conventional cultivation
Up to the time of reporting a total of 90 samples of conventionally pro-
duced table grapes from various countries were analyzed at CVUA
Stuttgart for approximately 600 different pesticides. Among these were 24
samples (27%) from Germany. Pesticide residues were detected in 88 of
the 90 (98%) table grapes from conventional cultivation (98% in 2011;
96% in 2010; 100% in 2009).
Samples from foreign soil: Two samples from Turkey and one
from South Africa were found to contain pesticides exceeding the
MRL. From the 64 samples originating from foreign countries, the
ADRESS Schaflandstraße 3/2 70736 Fellbach Germany E-MAIL Poststelle@cvuas.bwl.de
TELEFONE +49 711 3426 - 1234 INTERNET www.cvua-stuttgart.de
+49 711 3426 - 1727 (Diagnostics)
FAX +49 711 588176 +49 711 3426-1729 (Diagnostics)
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rate of MRL violations was 5% in 2012 (1% in 2011; 6% in 2010;
6% in 2009).
Local samples: The local samples were primarily obtained from
small producers or direct marketers; 22 of the 24 analyzed grapes
came from Baden-Württemberg. Violations of the MRL were de-
tected in 5 of the 24 local samples, two of which were from Rhein-
land-Pfalz. This corresponds to a rate of 21% (16% in 2011; 15%
in 2010; 76% in 2009).
Gratifying results: None of the 90 samples contained active sub-
stances over the acute reference dose (ARfD) established for
small children (in 2009 an exceedance of the ARfD was found in 5
of the 145 analyzed samples). Therefore, none of the samples
were classified as a health concern.
Investigations showed that 89% of the grapes contained several
different substances (multiple residues) per sample. On average
one grape sample contained 7.3 different substances, with an av-
erage quantity of 0.45 mg pesticides/kg grapes. (Values in 2011
were 6.3 substances and 0.55 mg/kg; 2010: 5.5 substances and
0.52 mg/kg; 2009: 5.9 substances and 0.62 mg/kg).
In 10 (42%) of the samples from local cultivation substances were
detected that are not authorized in Germany for use in table
grapes. These included the substances captan (1x), dimethomorph
(4x), dithianon (4x), folpet (5x), indoxacarb (1x), iprovalicarb (2x)
und spiroxamin (1x). It is suspected that in some of the cases so-
called wine grapes (used for making wine) were redesignated as
table grapes (those eaten directly). The resulting MRL violations
occurred because table grapes have stricter limits on pesticides
than wine grapes, both in quantity and type. Nevertheless, in 2012
no samples of local grapes were found with pesticides that are
completely forbidden in Germany, for all foods.
Table grapes from organic cultivation
Up to the time of reporting a total of 26 samples of organically produced
table grapes from various countries were analyzed (2 of which were grown
in Germany). No residues of chemical/synthetic pesticides were detected
in 15 of the analyzed grape samples. In the remaining 11 samples only
traces of residues were found. Of these, 7 contained residues of the insec-
ticide spinosad, which is authorized for use in organic cultivation under the
EU regulation for organic farming.
With regard to pesticides, all of the inspected organic table grapes fulfilled
the requirements for organic cultivation.
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Conclusion and Evaluation
The results of the investigations show that conventionally produced table
grapes were among the fruits with higher levels of contamination from
pesticides this year as well. As many as 98% of the analyzed table grape
samples contained pesticide residues. The number of samples in violation
of the MRL rose again in comparison to the previous year, reaching the
same high level as in 2010 (9% in 2012, 3% in 2011, 9% in 2010). The
acute reference dose (see Info Box, pg. 6) determined for small children
was not exceeded in any cases. Thus, no samples were categorized as a
health concern.
All of the five locally produced grape samples that violated the MRL con-
tained substances in quantities greater than 0.01 mg/kg; moreover, these
pesticides are unauthorized in Germany for use in table grapes (violation
of the authorized indications code). These included 4 cases of folpet and 1
case of captan. Grapes that are treated with pesticides containing
folpet may not be marketed as table grapes for direct consumption.
The percentage of samples exceeding the MRL, as well as the num-
ber of locally produced grape samples with residues of unauthorized
pesticides has increased again this year, and is still unacceptable.
The official food inspections will therefore be accordingly intensified
in the following season.
All of the 26 organically produced table grape samples were in line with
the EU regulations for organic farming.
Infobox
Differentiation between table grapes and wine grapes
Especially for locally grown grapes, the distinction between wine grapes (for
making wine) and table grapes (for direct consumption) doesn’t seem to be
i
completely understood. Grapes that are offered at food stands, farmer’s mar-
kets, grocery stores or supermarkets are for direct consumption and are classi-
fied and judged under food law as table grapes.
The difference is important because some pesticides, including those that are
toxicologically relevant, are only authorized for application in wine grapes, not
for table grapes. This is because wine making procedures such as pressing,
fermentation and purification naturally remove a large portion of pesticide resi-
dues. Therefore, to ensure consumer safety, grapes that are eaten directly
must have different MRLs than those for wine grapes.
Detailed Results for Table Grapes from Conventional Cultiva-
tion
Illustration 1 depicts the current situation regarding residues detected in
the 90 samples of table grapes from conventional cultivation. A total of
98% of the conventionally produced table grapes analyzed during this
reporting period contained residues of at least one substance; only two
were residue-free.
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9% 2%
no residues detected
with R < MRL
with R > MRL
89%
2012
Illustration 1: Pesticide residues in table grapes from conventional cultivation (CVUA
Stuttgart, 2012); R = Residues; MRL = Maximum residue limit according to EU Regulation
Nr. 396/2005.
Table 1 gives an overview of the results from the residue analyses. From
the 90 samples of conventionally produced table grapes 8 were in viola-
tion of the MRL. Of these 8 samples, 5 were local products, 2 came from
Turkey, and one was from South Africa. The guilty substances found in
the locally produced grapes included captan (1x), cyazofamid (1x) and
folpet (4x). While the substance captan is not permitted in Germany for
either table- or wine grapes, the substance folpet is authorized for use
only on wine grapes. The substance cyazofamid is permitted for table
grapes in Germany. Though the EU-established maximum limits for cap-
tan und cyazofamid are the same for table- and wine grapes (0.02 mg/kg
and 0.5 mg/kg respectively), this is not so for folpet. The maximum limit for
this substance is significantly lower for table grapes (0.02 mg/kg) than for
wine grapes (5 mg/kg).
A positive note is that in the reporting year of 2012 not a single sample
was found with residues over the acute reference dose determined for
small children. Therefore, none of the samples were categorized as being
a health concern.
Seite 5 von 11
Infobox
Acute Reference Dose, ARfD
Using the ADI (acceptable daily intake) to evaluate plant protection substances
that are highly toxic and whose intake even once or over a short time can have
health-threatening effects has limited value. Because the ADI has been derived
from longer-term studies, the characterization of an acute danger resulting from
residues in the diet would probably be insufficient. Therefore, in addition to the
ADI value an additional exposure limit has been established, the so-called
acute reference dose (ARfD). The World Health Organization defined the ARfD
i
as the amount of a substance one can consume within one day or with a meal
without resulting in a known health risk for the consumer. Unlike the ADI, the
ARfD value is not designated for every pesticide, but rather only for those sub-
stances that, when taken in a large enough quantity, can damage ones health
with just one case of exposure.
Source:
Grenzwerte für die gesundheitliche Bewertung von Pflanzenschutzmittelrück-
ständen.pdf (Bundesinstitut für Risikobewertung - BfR) (Limit Values for the
Assessment of Pesticide Residues on Health, from the National Institute of Risk
Assessment (BfR))
Model of Consumption for Children, Information Nr. 016/2005 of the BfR from 2
May, 2005 (www.bfr.bund.de)
Seite 6 von 11
Table 1: Pesticide Residues in Table Grapes from Conventional Cultivation by
Land of Origin (CVUA Stuttgart, Jan. - Oct., 2012)
No. With With Multiple Samples Substances
Origin
Samples Residues Residues > MRL > MRL
1x Captan,
1x
24 22 (92%) 22 (92%) 5 (21%) Cyazofamid,
Germany
4x Folpet
Europe
Italy 9 9 (100%) 8 (89%) 0 -
Greece 6 6 (100%) 6 (100%) 0 -
Spain 3 3* 3* 0 -
India 7 7 (100%) 7 (100%) 0 -
Asia
2x Car-
bendazim,
Turkey 5 5* 5* 2* 1x Chlorotha-
Table grapes 2012
lonil
South Africa 12 12 (100%) 8 (67%) 1 (8%) 1x DDAC&
Africa
Egypt 4 4* 4* 0 -
Namibia 3 3* 2* 0 -
Morocco 1 1* 1* 0 -
America
Chile 9 9 (100%) 9 (100%) 0 -
Argentine 5 5* 3* 0 -
Unknown 2 2* 2* 0 -
TOTAL 90 88 (98%) 80 (89%) 8 (9%) 10
For Comparison**:
2011 124 98% 93% 3% 4
2010 138 96% 88% 9% 14
2009 148 100% 93% 16% 35
2008 101 96% 87% 8% 8
2007 128 95% 86% 9% 15
2006 139 96% 88% 10% 14
2005 122 98% 86% 12% 18
2004 138 91% 76% 24% 38
MRL = Maximum limit according to EU Regulation Nr. 396/2005; *Data pool too
small for calculating averages. **The comparability of these data with each other
is limited in that the number of countries investigated in the various years was
inconsistent.
&
Since there is no specific MRL established for the substance DDAC in the EU
Regulation Nr. 396/2005, the general MRL of 0.01 mg/kg is valid, in accordance
with Article 18, Paragraph 1b of the EU Regulation Nr. 396/2005. Meanwhile, the
EU has assigned a value of 0.5 mg/kg for DDAC (didecyldimethylammonium chlo-
ride); this value was not exceeded in the current samples. Contamination from
DDAC can occur in various ways, e.g. via application as a pesticide or through
cross-contamination, because it is also authorized for use as a disinfectant. Be-
cause it is often difficult to identify the source of DDAC residues, the assigned
value of 0.5 mg/kg provides businesses as well as food controllers a transitional
measure for managing the marketing of products with a quantity of < 0.5 mg/kg of
benzalkonium chloride (BAC). This low level is assumed to be safe for one’s
Seite 7 von 11
health. For more information, see the Internet article (in German) „Rückstände
von quartären Ammoniumverbindungen (QAV) in frischem Obst und Gemüse –
Herkunft und Befunde“. (Residues of Quarternary Ammonium Compounds (QAC)
in Fruits and Vegetables – Origin and Findings)
Unauthorized Substances
In addition to controlling for the observance of the legal maximum residue
limits, locally cultivated products in which residues are detected are also
analyzed for the presence of substances not permitted in Germany (see
Info Box „Authorized Indications“). In 2012 all of the five samples of locally
produced table grapes that violated the MRL were also found to contain
folpet (4X) and captan (1X) in quantities > 0.01 mg/kg. These substances
are not authorized for use in Germany, and therefore are in violation of the
authorized indications code. A further five local samples that did not ex-
ceed the MRL were, nevertheless, also in violation of the code. Residues
of the active substances dimethomorph (4x), dithianon (4x), folpet (1x),
indoxacarb (1x), iprovalicarb (2x) und spiroxamine (1x) were detected (see
Table 2).
Table 2: Unauthorized Substances in German Table Grapes from Conventional
Cultivation in Comparison to Previous Years (CVUA Stuttgart, Jan.- Oct., 2012
and 2009-2011)
Samples Not Author-
Samples w/ Substances Samples w/ Substances
No. ized for this Culture
Year Not Authorized in Ger- Not Authorized for this
Samples (some multiple sub-
many Culture
stances per sample)
Captan,
4x Dimethomorph,
4x Dithianon,
2012 24 0 10 (42%) 5x Folpet,
Indoxacarb,
2x Iprovalicarb,
Spiroxamin
Azoxystrobin,
2011 19 0 4 (21%) 3x Folpet,
Spiroxamin
Fluquinconazol,
1 (3%) 8 (21%) 5x Folpet,
2010 39 Indoxacarb,
Endosulfan 2x Spiroxamin
Captan
15 x Folpet (2x ARfD
1 (5%) above 100%)
2009 21 16 (76%) 2x Indoxacarb
Oxydemeton-methyl
(ARfD above 100%) 6x Iprovalicarb
2x Metalaxyl
1x Spiroxamin
Infobox
Authorized Indications (§ 12 Pesticide Regulation)
i The authorized indications code has been valid for all pesticides since July 1,
2001, and states that the substances in question are permitted. However,
these may only be employed within the scope stipulated by the Federal Agency
for Consumer Protection and Food Safety (BVL). The databank of the author-
ized substances can be
https://portal.bvl.bund.de/psm/jsp/).
found on the BVL’s website:
Seite 8 von 11
Multiple Pesticides
As presented in Table 1, 89% of the conventionally produced table grapes
were found to contain more than one substance per sample (multiple resi-
dues). Illustration 2 shows that the frequency distribution is very wide,
ranging from 0 to a high of 23 substances detected in one sample. In 2012
analyses revealed an average number of 7.3 substances per sample. The
average quantity per pesticide was 0.45 mg/kg. As seen in Table 3, the
grapes analyzed in 2012 were found on average to contain a higher num-
ber of different substances per sample, but a lower quantity of each pesti-
cide in comparison to previous years.
10
9
8
7
Number of Samples
6
5
4
3
2
1
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23
Number of Substances
Illustration 2: Frequency distribution of multiple residues in table grapes from conventional
cultivation (CVUAS Jan. - Oct., 2012). All values above the LOQ (limit of quantification)
were used.
The existence, form and quantity of these multiple residues indicates the
employment of so-called combination preparations (using several sub-
stances) as well as myriad different preparations used to protect plants
from illnesses and pests. Because authorization of particular substances
may change, expire or be added to, the spectrum of substances is in con-
stant flux. In order to maintain an accurate picture of the status of food
contamination via official food control it is especially important that new
analytical methods are continuously developed so that new substances
can be detected.
Seite 9 von 11
Table 3: Pesticide Residues in Table Grapes from Conventional Cultivation, by
Year (CVUA Stuttgart Jan. - Oct., 2012 and 2006 to 2011)
Average
Average No. Sub- Maximum No. Different
Pesticide Con-
Year stances No. Substances per Substances
tent
per Sample Sample Found
[mg/kg]
2012 0.45 7.3 23 81
2011 0.55 6.3 23 84
Table grapes
2010 0.52 5.5 16 83
2009 0.62 5.9 24 88
2008 0.32 4.0 19 63
2007 0.40 4.7 12 71
2006 0.48 6.4 21 82
As Table 4 shows, the locally produced table grapes were less contami-
nated with pesticide residues than those from Asia and South America
(0.39 mg/kg vs. 0.90 and 0.51 respectively). Only the grapes from Africa
were minimally contaminated. Grapes from Turkey contained an average
of 16.4 substances per sample, and presented the highest level of pesti-
cide content, at 2.0 mg/kg.
Table 4: Pesticide Residues in Table Grapes from Conventional Cultivation, by
Land of Origin (CVUA Stuttgart Jan. - Oct., 2012)
Europe
Africa Asia America Germany
(w/o G.)
Average no.
Table grapes
substances per 4.6 12.2 5.4 6.8 8.4
sample
Average quantity
of pesticide 0.17 0.90 0.51 0.40 0.39
[mg/kg]
Maximum no.
substances per 12 23 11 13 15
sample
Spectrum of Active Ingredients
Among the conventionally produced table grapes analyzed this year, a
total of 81 different substances were detected. When one compares these
data with those of previous years, the higher differentiation can have vari-
ous causes, although the previous discussion of the ever-expanding spec-
trum of substances and their accompanying regulations, as well as the
further development of analytical methods, all make a significant contribu-
tion. Equally significant are such aspects as land of origin and time of
year. An overview of the 50 most commonly detected substances from the
spectrum of active ingredients is presented in Table 5. Fungal disease
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poses a serious problem for grape production, which is reflected in the
spectrum of active ingredients: the most frequently detected residues were
those of fungicides.
Table 5: Spectrum of active ingredients in table grapes from conventional cultiva-
tion: the 50 most frequently detected substances, including those with exceed-
ances of the MRL (CVUA Stuttgart Jan. - Oct. 2012). Whereas all values above
the LOQ (limit of quantification) were used.
No. Samples w/ Maximum No. Samples w/
Active Ingredient
Residues (mg/kg) Residues > MRL
1 Boscalid (F) 41 1.5 0
2 Cyprodinil (F) 35 0.26 0
3 Myclobutanil (F) 35 0.14 0
4 Fludioxonil (F) 30 0.16 0
5 Penconazole (F) 29 0.15 0
6 Imidacloprid (I) 26 0.18 0
7 Quinoxyfen (F) 26 0.023 0
8 Fenhexamid (F) 23 1.1 0
9 Dimethomorph (F) 21 0.66 0
10 Pyrimethanil (F) 19 1.4 0
11 Chlorpyrifos (I) 18 0.087 0
12 Trifloxystrobin (F) 17 0.14 0
13 Cyazofamid (F) 16 0.59 1
14 Metrafenone (F) 16 0.13 0
15 Famoxadone (F) 15 0.15 0
16 Kresoxim-methyl (F) 14 0.03 0
17 Spinosad* (I) 13 0.04 0
18 Iprodione (F) 13 0.45 0
19 Azoxystrobin (F) 12 0.22 0
20 Methoxyfenozide (I) 12 0.47 0
21 Pyraclostrobin (F) 12 0.024 0
22 Fluopicolide (F) 11 0.028 0
23 Folpet (F) 11 0.16 4
24 Indoxacarb (I) 11 0.2 0
25 Tebuconazole (F) 11 0.16 0
26 Iprovalicarb (F) 10 0.022 0
27 2.6-Dichlorobenzamide 9 0.008 0
28 Fluopyram (F) 9 0.095 0
29 Spiroxamine (F) 9 0.077 0
30 Ethephon (W) 8 0.21 0
31 Metalaxyl/Metalaxyl M (F) 8 0.32 0
32 Dithianon (F) 7 0.3 0
33 Carbendazim* (F) 6 0.75 2
34 Lambda-Cyhalothrin (I) 6 0.16 0
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35 Proquinazid (F) 6 0.022 0
36 Chlorpyrifos-methyl (I, A) 5 0.013 0
37 Spirotetramat* (I) 5 0.13 0
38 Cyflufenamid (F) 4 0.007 0
39 Forchlorfenuron (W) 4 0.004 0
40 Spirodiclofen (A) 4 0.009 0
41 Tetraconazole (F) 4 0.087 0
42 Thiamethoxam* (I) 4 0.036 0
43 Chlorantraniliprole (I) 3 0.052 0
44 Fenoxycarb (I) 3 0.008 0
45 Flusilazole (F) 3 0.008 0
46 Hexaconazole (F) 3 0.005 0
47 Methiocarb* (I, A) 3 0.013 0
48 Triadimefon/Triadimenol* (F) 3 0.038 0
49 Zoxamide (F) 3 0.06 0
50 Bupirimate (F) 2 0.034 0
...
Captan 2 0.22 1
Chlorothalonil 2 1.2 1
Didecyldimethylammonium
chlorid 1 0.063 1
* = Total parameter; F = Fungicide; I = Insecticide; A = Acaricide; G = Growth regulator
Photo Credits:
Süß und saftig an der Rebe (“Sweet and Juicy on the Vine”), Marianne J.,
Pixelio.de, Image-ID=603575.
Author(s):
Kathi Hacker, Ellen Scherbaum.
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